Polyamide containing organo metallic compound

ABSTRACT

Synthetic fiber and film forming polyamides containing organic compounds of metals of groups IV or V of the Periodic Table. The pressure of such compounds results in an increase in the rate of relative viscosity rise during the polyamidation reaction and an enhancement of the dyeability of the final polymer.

United States Patent James 1 Dec. 5, 1972 [72] Inventor: David James, Pontypool, England [73] Assignees Imperial Chemical Industries Limited, London, England 22 Filed: July 24, 1970 [2]] Appl. No.: 58,185

[52] US. Cl ..260/78 R, 260/78 L 51 1 1m. Cl. ..C08g 20/20 [58] Field of Search ..260/78 R, 78 A, 78 L, 78 P,

' 260/78 S, 78 SC [56] References Cited UNITED STATES PATENTS 3,153,010 10/1964 Jenkins et-al. ..260/78 R 3,160,609 12/ l 964 Congiondi et al ..260/78 R 3,160,610 12/1964 Congiondi et a1 ..260/78 R 3,272,776 9/1966 Caldwell ..260/78 R 2,924,586 2/1960 Lotz et al ..260/78 SC 3,189,575 6/1965 l-Iorn et al ..260/78 SC 3,405,099 10/1968 Taber ..260/78 P FOREIGN PATENTS OR APPLICATIONS 684,876 2/1968 Japan OTHER PUBLICATIONS Chemical Abstracts- Vol. 70, 1969. p. 48052r Primary Examiner-Harold D. Anderson Attorney-Thomas J. Morgan and Stephen D. Murphy 57 9 ABSTRACT Synthetic fiber and film forming polyamides containing organic compounds of metals of groups IV or V of the Periodic Table. The pressure of such compounds results in an increase in the rate of relative viscosity rise during the polyamidation reaction and an enhancement of the dyeability of the final polymer.

5 Claims, No Drawings POLY AMIDE CONTAINING ORGANO METALLIC COMPOUND The present invention relates to synthetic polyamides and particularly, thoughv not exclusively, to synthetic fiber and film forming polyamides containing organic metal compounds.

The Applicants have found that the use of certain organic metal compounds in the production of synthetic polyamides and their subsequent presence in the polymer can give rise to a number of beneficial effects. These effects include an increase in the rate of relative viscosity rise during the polymerization reaction and an enhancement of the dyeability of the resultant polymer.

By relative viscosity is meant the ratio of the viscosity of a solution of the polymer to the viscosity of the pure solvent.

Synthetic fiber and film forming polyamides to which the present invention is applicable include both homoand copolyamides, e.g. those, derived from polyhexamethylene adipamide, I polyhexamethylene suberamide and polycaprolactam.

Organic compounds suitable for use in the present invention include those of the following general formulas:

R OR

where M represents a metal of groups IV or V of the Periodic Table, R is an alkyl group and R an alkyl or aryl group.

OOO

where M represents a metal of groups IV or V of the Periodic Table and R is an alkylene or arylene group.

Specifically M may be titanium, zirconium, hafnium, vanadium, niobium, or tantalum.

Alternatively polymeric derivatives of the above organic compounds may be employed, either separately or in conjunction with the monomer.

Thus, the present invention provides a synthetic polyamide composition containing one or more organic compounds of titanium, zirconium, hafnium, vanadium, niobium or tantalum.

The invention also provides a process for increasing the rate of relative viscosity rise during a polyarnidation reaction by the addition thereto of one or more organic compounds of titanium, zirconium, hafnium, vanadium, niobium or tantalum.

The invention further provides a process for enhancing the dyeability of synthetic polyamides by the addition thereto before or during the polyarnidation reaction of one or more organic compounds of titanium, zirconium, hafnium, vanadium, niobium or tantalum.

Up to 10 mole percent of organic metal compound or compounds may be added before or during the early stages of polymerization, though it is preferred to add 0.1 to 3 mole percent of the metal compound or compounds.

Preferably, the polyamide composition is capable of being melt-spun into continuous filaments and contains an organic compound of titanium.

The organic metal compounds of the present invention possess the further advantage, that, unlike conventional acid polyamidation catalysts which can catalyze hydrolysis of the polyamide and consequently may promote the degradation of the polymer under even mild hydrolytic conditions, they are converted to inactive metal hydroxides after heating the polyamide for quite short periods or on subjecting the polymer to mild hydrolytic conditions. Moreover, conventional acid catalysts being ionic in'character oftenhave an undesirable coagulating effect on fine dispersions of pigments, delustrants and the like, which may be added to polyamides. The organic metal compounds of the present invention are much more compatible with these and other polymer additives.

In the following examples of the present invention which are by way of illustration only, parts and percentages are by weight.

EXAMPLE 1 TABLE 1 Relative Viscosity Time of finishing" under steam at Polyhexamethylene 290C (min.) Polyhexamethylene adipamide 1.4

adipamide control mol tetra-iso propyl titanate Branch chain alkyl titanates are even more effective than their linear homologues. This is shown in Table 2, where a comparison of the effect of tetra-n-butyl and tetra-t-butyl titanates on the rate of polymerization of hexamethylene adipamide has been made.

TABLE 2 relative viscosity test minus Time of finishing" relative viscosity control at 290C under steam (min.) 1.4 mol tetra-n- 1.4 mol tetra-tbutyl titanate butyl titanate EXAMPLE 2 rate of polymerization is further increased as shown in Table 5.

TABLE Time offinishing" at 290C under relative viscosity test minus relative viscosity control steam (min.)

Effect of tetra-alkyl titanates on the rate of 0 polymerization of hexamethylene suberamide.

Polyhexamethylene suberamide pre polymers containing 0.67, 0.92 and 1.2 mole percent of tetra-methyl titanate were finished in a laboratory pot at 290 C. for 1 hour under steam at atmospheric pressure. A control polyamide without additive was simultaneously finished under the same conditions in a similar pot. The relative viscosity of the four polymers after fmishing is given in the Table below. As will be seen, the presence of the alkyl titanate had a significant effect on the rate of amide polymerization.

TABLE 3 Relative Viscosity Polymer after "finishing Polyhexamethylene suberamide control (no additive) Polyhexamethylene suberamide 0.67 mole of tetramethyl titanate Polyhexamethylene suberamide 0.67 mole of tetramethyl titanate Polyhexamethylene suberamide 1.2 mole of tetramethyl titanate 58 EXAMPLE 3 TABLE 4 Fully polymerized polyhexamethylene adipamide; (Carboxylic end groups C concentration of methyl minus amine end groups A) titanate mol per g. of polyamide.

EXAMPLE 4 The base stabilized nature of the polyhexamethylene adipamide of this invention may be counteracted by the addition prior to the polymerization reaction, of the requisite amount of adipic acid. When this is done, the

Base-stabilized polymer contain- Balanced endgroup polymer ing 0.7 mol containing 0.7 tetra-methyl mol tetratitanate methyl titanate EXANIPLE 5 Effect of tetra-aryl titanates on the rate of polymerization of hexamethylene adipamide.

Example 1 was repeated with the exception that the tetra-iso-propyl titanate was replaced by tetra-phenyl titanate.

As can be seen from Table 6, tetra-phenyl titanate also has a marked effect on the polymerization rate.

TABLE 6 Time of Relative Viscosity "finishing under steam at 290C Polyhexamethylene Polyhexamethylene (min.) adipamide control adipamide 1.8

mol tetra-phenyl titanate EXAMPLE 6 Example 1 was again repeated with the exception that the tetra-iso-propyl titanate was replaced by tetran-butyl zirconate. As with Example 1 the presence of the zirconate had a significant effect upon the rate of polymerization as shown in Table 7.

TABLE 7 Time of Relative Viscosity finishing" under steam Polyhexamethylene Polyhexamethylene at 290C adipamide control adipamide 0.86 min.) mol tetra-nbutyl zirconate EXAMPLE 7 Effect of poly alkyl titanates on the rate of polymerization of hexarnethylene adipamide.

Example 1 was repeated with the exception that tetra-iso propyl titanate was replaced by poly-n-butyl titanate.

As can be seen from Table 8, poly-n-butyl titanate also has a noticeable effect on the polymerization rate.

TABLE 8 Time of Relative Viscosity "finishing" under steam polyhexamethypolyhexamethypolyhexamethyat 290C lene adipamide lene adipamide lene adiparnide 5 (min.) control 1.1 mol +1.5 mol poly-n-butyl poly-n-butyl titanate titanate EXAMPLE 8 Effect of di-alkoxy di-acylated titanates on the rate of polymerization of hexamethylene adiparnide.

The method outlined in Example 2 was repeated with the exception that 0.6 mole percent of di-isopropoxy titanium distearate was used.

A similar useful effect was observed as shown below:

TABLE 9 Polymer relative viscosity Polyhexamethylene adipamide control (no additive) 47 Polyhexamethylene adipamide 0.6

mole di-isopropoxy titanium 69.6

diutearate What I claim is:

1. A synthetic linear saturated aliphatic polycarbonamide of a dicarboxylic acid and a diarnine, said polycarbonamide having an increased depth of dyeing and being capable of being spun into continuous filaments, said polyamide containing from 0.1 to 10 mol percent of one or more organic compounds selected from the wherein R is an alkyl or aryl group, R is an alkyl group, R" is an alkylene or arylene group and M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum. 2. The polycarbonamide of claim 1 wherein said organic compounds have the following general formula:

wherein R is an alkyl or aryl group and M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum.

3. The polycarbonamide of claim 1 wherein said organic compounds have the following structural formula:

wherein R is an alkyl or aryl group, R is an alkyl group and M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum.

4. The polycarbonamide of claim 1 wherein said organic compounds have the following structural formula:

OCC

wherein R is an alkylene or arylene group and M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum.

5. The polycarbonamide of claim 1 wherein M is titanium. 

2. The polycarbonamide of claim 1 wherein said organic compounds have the following general formula: wherein R is an alkyl or aryl group and M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum.
 3. The polycarbonamide of claim 1 wherein said organic compounds have the following structural formula: wherein R is an alkyl or aryl group, R'' is an alkyl group and M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum.
 4. The polycarbonamide of claim 1 wherein said organic compounds have the following structural formula: wherein R'''' is an alkylene or arylene group and M represents a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and tantalum.
 5. The polycarbonamide of claim 1 wherein M is titanium. 